A density functional theory for studying ionization processes in water clusters.
A density functional theory for studying ionization processes in water clusters.
复制标题
用于研究水团簇电离过程的密度泛函理论。
DOI：
10.1021/jp1057572
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
R. Baer
中科院分区：
文献类型：
--
作者：
Ester Livshits;Rebecca Granot;R. Baer
基于Baer-Neuhauser-Livshits距离分离杂化理论，采用广义Kohn-Sham（GKS）密度泛函理论方法，结合从头算激发的距离参数调谐，研究了水二聚体和五聚体阳离子的性质.水二聚体首先被用作基准系统来检查该方法。目前品牌的DFT本地化的正电荷（孔），稳定的质子转移几何与最近的耦合集群计算。水二聚体阳离子的各种构象的相对能量比较以及与以前发表的耦合集群的结果。GKS轨道能量是很好的近似系统的实验电离势。基于本方法的含时密度泛函理论计算的低激发能与最近发表的高水平“运动耦合簇方程”计算结果相比较。水二聚体阳离子的谐波频率与实验和波函数计算结果吻合良好。将该方法应用于水五聚体阳离子的研究。确定了三种构象：两种是本征型，一种是Zundel型。分析了其结构和谐振结构。五聚体水簇在0 K下的电离动力学显示出快速<50 fs的瞬态，用于从其中一个水分子转移质子，释放羟基自由基并产生携带过量空穴的质子化四聚体。
A generalized Kohn-Sham (GKS) approach to density functional theory (DFT), based on the Baer-Neuhauser-Livshits range-separated hybrid, combined with ab initio motivated range-parameter tuning is used to study properties of water dimer and pentamer cations. The water dimer is first used as a benchmark system to check the approach. The present brand of DFT localizes the positive charge (hole), stabilizing the proton transferred geometry in agreement with recent coupled-cluster calculations. Relative energies of various conformers of the water dimer cation compare well with previously published coupled cluster results. The GKS orbital energies are good approximations to the experimental ionization potentials of the system. Low-lying excitation energies calculated from time-dependent DFT based on the present method compare well with recently published high-level "equation of motion-coupled-cluster" calculations. The harmonic frequencies of the water dimer cation are in good agreement with experimental and wave function calculations where available. The method is applied to study the water pentamer cation. Three conformers are identified: two are Eigen type and one is a Zundel type. The structure and harmonic vibrational structure are analyzed. The ionization dynamics of a pentamer water cluster at 0 K shows a fast <50 fs transient for transferring a proton from one of the water molecules, releasing a hydroxyl radical and creating a protonated tetramer carrying the excess hole.
影响因子：
15
作者：
Adriaanse, Christopher;Sulpizi, Marialore;Sprik, Michiel
通讯作者：
Sprik, Michiel